Photochemically initiated oxidative carbon-carbon bond-cleavage reactivity in chlorodiketonate Ni(II) complexes.

Three mononuclear Ni(II) complexes containing a 2-chloro-1,3-diketonate ligand and supported by the 6-Ph(2)TPA chelate, as well as analogues that lack the 2-chloro substituent on the β-diketonate ligand, have been prepared and characterized. Upon irradiation at 350 nm under aerobic conditions, complexes containing the 2-chloro-substituted ligands undergo reactions to generate products resulting from oxidative cleavage, α-cleavage, and radical-derived reactions involving the 2-chloro-1,3-diketonate ligand. Mechanistic studies suggest that the oxidative cleavage reactivity, which leads to the production of carboxylic acids, is a result of the formation of superoxide, which occurs through reaction of reduced nickel complexes with O(2).

Synthesis and characterization of iron(II) quinaldate complexes.

Treatment of iron(II) chloride or iron(II) bromide with 2 equiv of sodium quinaldate (qn = quinaldate or C(10)H(6)NO(2)(-)) yields the coordinatively unsaturated mononuclear iron(II) quinaldate complexes Na[Fe(II)(qn)(2)Cl].DMF and Na[Fe(II)(qn)(2)Br].DMF (DMF = N,N-dimethylformamide), respectively.